Production of polymers with a fibrous structure

ABSTRACT

POLYMERS HAVING A FIBROUS STRUCTURE ARE OBTAINED BY THE POLYMERIZATION OF SOLUTIONS AND/OR EMULSIONS OR DISPERSIONS FULLY OR PARTIALLY SOLIDIFIED IN CRYSTALLINE FORM, OF ETHYLENICALLY UNSATURATED MONOMERS WITH AT LEAST TWO POLYMERIZABLE DOUBLE BONDS OR MIXTURES CONTAINING AT LEAST 0.01% WEIGHT OF THESE MONOMERS AND MONOETHYLENICALLY UNSATURATED MONOMERS BY IRRADIATION, WHICH POLYMERS CAN BE OBTAINED IN THE FORM OF NOVEL POROUS MATERIALS(=POROMERIC MATERIALS) HAVING PROPERTIES SIMILAR TO LEATHER.

United States Patent Office 3,778,294 Patented Dec. 11, 1973 3,778,294PRODUCTION OF POLYMERS WITH A FIBROUS STRUCTURE Carl Heinrich Krauch,Heidelberg, and Axel Sanner, Ludwigshafen (Rhine), Germany, assignors toBadische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine),Germany No Drawing. Original application July 16, 1968, Ser. No.745,113. Divided and this application Sept. 22, 1971, Ser. No. 182,860Claims priority, application Germany, July 22, 1967, P 17 20 286.7; Feb.24, 1968, P 17 20 350.8; May 30, 1968, P 17 70 528.1, P 17 70 529.2; May31, 1968, P 17 70 543.0; June 1, 1968, P 17 70 552.1

Int. Cl. B44d 1/50; D06m 13/20 U.S. Cl. 117-93.31 11 Claims ABSTRACT OFTHE DISCLOSURE Polymers having a fibrous structure are obtained by thepolymerization of solutions and/or emulsions or dispersions fully orpartially solidified in crystalline form, of ethylenically unsaturatedmonomers with at least two polymerizable double bonds or mixturescontaining at least 0.01% by weight of these monomers andmonoethylenically unsaturated monomers by irradiation, which polymerscan be obtained in the form of novel porous materials (=poromericmaterials) having properties similar to leather.

The present application is a division of application Ser. No. 745,113,which was filed on July 16, 1968.

The invention relates to a process for the production of polymers havinga fibrous structure, in which ethylenically unsaturated monomers arepolymerized by irradiation.

It is known that ethylenically unsaturated monomers may be convertedinto polymers by irradiation. Sensitizers are frequently used in suchprocesses and in general the processes are carried out at roomtemperature. The monomers are generally present in liquid form, that isin solution or as a liquid substance. It is also known to polymerizeethylenically unsaturated monomers, which are present in crystallineform, in bulk. Finally, it is known to carry out the polymerization ofmonoethylenically unsaturated monomers, such as acrylonitrile,acrylamide and vinyl pyrrolidone in solution solidified in amorphousform, for example castor oil. Conventional polymers, which are generallypresent in the form of powders or gels, are obtained by using theseknown processes, which are summarized in Chapter 4 of the book ActionsChimiques et Biologiques des Radiations, th Series, Masson & Cie.,Editeurs, Paris, 1966. An exception is the polymerization of puremethacrylic acid crystals by UV-irradiation, in which there is formedwithin the same crystal in addition to the amorphous polymer a smallamount of fibrous polymer. (C. H. Bamford, A. D. Jenkins and J. C. Ward,J. Polym., 37, 48 (1966). Furthermore, French Pat. 1,414,088 discloses aprocess for impregnating non-Woven fabrics with' aqueous polymerdispersions and cooling the impregnated non-Woven fabrics to atemperature at which setting of the aqueous polymer dispersion withinthe fabric takes place. This results in the freeze-agglomeration of thepolymer dispersions with fiber-like agglomerates being formed from thepolymers.

The object of the present invention is to produce polymers having afibrous structure by the direct polymerization of olefinicallyunsaturated monomers. A further object of this invention is to producepolymers with a fibrous structure arranged to form a porous, flatmaterial.

Further objects of the invention will be apparent to those skilled inthe art from the following detailed description. These objects can beachieved by the present invention.

It has been found that polymers with a fibrous structure are obtained bypolymerizing ethylenically unsaturated monomers in liquids which havebeen solidified by irradiation, by fully or partially solidifying incrystalline form solutions and/or emulsions or dispersions of monomerswith at least 2 polymerizable double bonds or mixtures of such monomersand monoethylenically unsaturated monomers, which contain at least 0.01and in particular at least 0.5% by weight of monomers with 2polymerizable double bonds, irradiating the solidified mass andseparating off the liquid. Surprisingly, with the new process, polymershaving a fibrous structure are obtained. When monoethylenicallyunsaturated monomers such as styrene, acrylonitrile or acrylic esters insolutions solidified in crystalline form are polymerized alone byirradiation, non-structured and generally gel-like polymers and notpolymers in fiber form are obtained.

For the new process nearly all polyethylenically unsaturated monomerscan be used which contain at least two polymerizable double bonds.Suitable compounds are, for example, polyethylenically unsaturatedcarboxylic esters, e.g. diesters of aliphatic or cycloaliphatic diolswith preferably 2 to 10, and preferably 2 to 6 C atoms, such as ethyleneglycol, propylene glycol, 1,4-butanediol, 1,6- hexanediol and1,4-cyclohexanediol and of monoethylenically unsaturated monocarboxylicacids, such as acrylic and methacrylic acids, e.g. ethyleneglycoldiacrylate and methacrylate, 1,4-butanediol diacrylate, methacrylate andcrotonate, 1,6-hexanediol diacrylate and 1,4-cyclohexanediol diacrylate,divinyl maleate, polyvinyl esters of polycarboxylic acids, in particulardivinyl esters of aliphatic or aromatic dicarboxylic acids, inparticular those containing from 4 to 8 C atoms and, if desired, oneolefinic double bond, such as divinyl oxalate, divinyl fumarate, divinyladipate and divinyl phthalate; vinyl esters of monoolefinicallyunsaturated monocarboxylic acids containing preferably 3 or 4 C atoms,such as vinyl methacrylate, vinyl crotonate and preferably vinylacrylate, allyl carboxylic acid esters, in particular saturated ormonolefinically unsaturated dicarboxylic acids containing 3 to 8 Catoms, such as diallyl phthalate allyl acrylate and methacrylate,diallyl maleate, diallyl oxalate, diallyl adipate,allyl-a-chloroacrylate and allyl-abromomethacrylate. Such unsaturatedcarboxylic acid esters generally have two or three olefinic double bondsand 5 to 20, and in particular 5 to 14 C atoms, and they may, ifdesired, be derived from substituted carboxylic acids, e.g. fromhalogenated carboxylic acids, in particular from monoethylenica'llyunsaturated monocarboxylic acids substituted in the a-position bybromine or chlorine.

Suitable compounds are furthermore polyethylenically unsaturatedhydrocarbons, such as butadiene, isoprene, 2,3-dimethylbutadiene anddivinylbenzene, containing preferably from 4 to 10 C atoms.

Suitable polyethylenically unsaturated monomers are in additionpolyethylenically unsaturated carboxylic acid amides, e.g. the diamidesof acrylic or methacrylic acid and diamines, in particular diaminescontaining from 2 to 6 C atoms, such as N,N-ethylene-bis-acrylamide andmethacrylamide and N,N-hexamethylene-bis-acrylamide, furthermorepolyethylenically unsaturated derivatives of melamine, dicyandiamine,urea and guanidine, such as N,N-diallyl melamine, triallylisocyanurate,tetramethylolacetylenediurea-tetraalyl ether,N,N-hexamethylene-bisallylurethane and N,N-xylylene-bis-allylurethane.

Suitable polyethylenically unsaturated compounds are furthermorepolyethylenically unsaturated amines, such as N,N-diallylamine, andpolyethylenically unsaturated heterocyclic compounds, such as2,5-divinylpyridine, 1,3,- divinylimidazole and 1,3-divinylcarbazole.

Particuluarly interesting polyethylenically unsaturated monomerscontaining at least 2 polymerizable double bonds are the so-calledunsaturated polyesters, which are customarily used in the production ofthe so-called unsaturated polyester resins and which are described, forexample, in the book by P. Selden Glasfaserverstiirkte Kunststotfe,Springer-Verlag, 1967, pages 8 to 18. They generally have linearmolecules with recurrin ester groups in the chain, at least twopolymerizable olefinic double bonds and molecular weights which aregenerally greater than 500 and frequently between 500 and 5000 or insome instances even higher, e.g. 8000. In manufacturing these polymersby the process described, for example, in the above-mentioned book by P.Selden, on pages 16 to 18, generally speaking equivalent orsubstantially equivalent amounts of aliphatic, cycloaliphatic oraromatic dicarboxylic acids, in particular Jr-ethylenically unsaturateddicarboxylic acids, which generally contain from 4 to 6 C atoms, oranhydrides thereof with diols, in particular with aliphatic,cycloaliphatic or araliphatic diols, which generally contain from 2 to22, and in particular from 2 to 12 C atoms and if desired ether oxygenatoms, are subjected to polycondensation. The unsaturated polyester canalso be condensed in smaller quantities, e.g. in amounts of 0.1 to 20%by weight with mono-, trior polybasic carboxylic acids and/or mono-,trior polyhydric alcohols in customary manner. The acid numbers of theappropriate unsaturated polyesters are generally between and 100 andpreferably between 5 and 60.

Suitable unsaturated polyesters are for example those of alkanediols,such as ethylene glycol, propylene glycol, 1,4-butanediol, alkenediols,such as 2-butene-l,4-diol, 3- butene-1,2-diol, ether oxygen containingalkane diols, such as diethylene glycol and triethylene glycol and/orfurthermore neopentyl glycol, and a,fi-ethylenically unsaturateddicarboxylic acids, in particular maleic acid, and furthermore fumaricacid, itaconic acid, mesaconic acid, citraconic acid, dihydromuconicacid, a-methyleneglutaric acid and endomethylenetetrahydrophthalic acid.Such unsaturated dicarboxylic acids are admixed with advantage with e.g.25-75% by weight, based on the total dicarboxylic acid content, ofdicarboxylic acids which do not contain copolymerizable double bonds,such as phthalic acid, dihydrophthalic acid, tetrahydrophthalic acid andadipic acid, in the production of the unsaturated polyester.

The amount of unsaturated polyesters can in general be between 2 and100, and preferably between 5 and 40% by weight, based on the totalmonomer content. In addition to the unsaturated polyesters othermonomers containing at least two double bonds may be admixed in desiredamounts. It is advantageous for at least 5% by weight of the entiremonomer content, the monomers containing at least two polymerizabledouble bonds, to be unsaturated polyesters. When the polyethylenicallyunsaturated monomers are unsaturated polyesters, polymers are obtainedwith a fibrous structure having very high fastness to rubbing andtensile strength.

It is particularly advantageous from the economic point of view in thecase of the new process to admix monoethylenically unsaturated monomerswith the polyethylenically unsaturated monomers. Suitable compounds forthis purpose are in particular acrylic esters and/ or methacrylicesters, in particular those of alkanols with 1 to 8,'

and in particular with 1 to 4 C atoms, e.g. the methyl, ethyl, n-butyl,isobutyl, n-hexyl, cyclohexyl and 2-ethylhexyl esters of acrylic andmethacrylic acid, and furthermore acrylonitrile and methacrylonitrile,monoolefins, in particular with 1 to C atoms, such as l-butene, 1-heptene, cyclopentene and norbornene, monovinylaromatic compounds suchas styrene, vinyltoluene and amethylstyrene, vinyl esters in particularthose containing saturated aliphatic carboxylic acids with 3 to 18 Catoms, such as vinyl acetate, vinyl propionate, vinyl laurate and vinylstearate, vinylidene halides, such as vinyl chloride, vinyl fluoride andvinylidene chloride, vinyl ethers, in particular of alkanols with 1 to 4C atoms, such as methyl vinyl ether and isobutyl vinyl ether,heterocyclic monovinyl compounds, such as N-vinyl caprolactam, vinylpyridine, N-vinyl imidazole, N-vinyl carbazole and N- vinyl pyrrolidone,furthermore in small amounts, in particular in amounts of 0.1 to 10% byweight, with regard to the total monomer content, monoethylenicallyunsaturated monocarboxylic aids, preferably with 3 to 4 C atoms and ifdesired substituted amides thereof, such as acrylic acid and methacrylicacid, acrylamide, methacrylamide, N-methylol acrylamide,N-methylolmethacrylacrylamide and alkyl ethers of such methylolcompounds, e.g. methyl and butyl ethers, and vinylsulfonic acids andalkyl esters and hydroxyalkyl acrylates and methacrylates thereof, suchas 1,4-butanediol monoacrylate, 2-hydroxyethyl acrylate,3-chloro-2-hydroxypropyl acrylate, in particular those containinghydroxyalkylene radicals with 2 to 6 C atoms.

The ethylenically unsaturated monomers of the new process can also bematerials which in addition to the polymerizable double bonds containchromophoric groups. Such colored monomers are for example dyes of theazo, anthraquinone and diarylmethane series containing a polymerizableCC double bond. A number of such dyes is for example described in GermanPats. 1,052,016, 1,107,356 and 1,136,302, in Austrian Pat. 211,447, inFrench Pat. 1,118,705 and in Belgian Pats. 566,099 and 590,317. Asexamples there may be mentioned the coupling products of diazotized1-amino-3- acryloylaminobenzene with 1-[N-(B-hydroxyethyU-N-(B-cyanoethyl)-amino] 3 methylbenzene or of diazotized 1-acryloylamino-4aminobenzene and 1 hydroxynaphthaline-4-sulfonic acid,acryloylaminobenzene, l-amino-Z- acetyl-4-acryloyl-amino-anthraquinone.The amount of such colored monomers is generally between 10 and 0.01,and preferably between 5 and 0.5% by weight, based on the total monomercontent. The photoinitiators and the sensitizing agents used generallyaffect the choice of the colored monomers must have an absorptionminimum in the range of the absorption maximum of the sensitizingagents. When the spectra of the colored monomers and of the sensitizingagent overlap and when consequently photoinitiation is unsuitable, theoperation is advantageously carried out With ionizing radiation.

In the production of mixed polymers from monomers with at least twopolymerizable double bonds and monomers with only one ethylenicallyunsaturated double bond, the ratio of the two monomeric substances canbe varied within a wide range, but there must be present in the mixtureat least 0.01 and in particular at least 0.5 by weight, based on thetotal monomer content, of monomers with at least two double bonds. Theamount of monomer with at least two polymerizable bonds is preferablyfrom 5 to 100% by weight, based on the total monomer content. Asmonomers with at least two double bonds, those with at least twopolymerizable double bonds are preferred. Of particular importance arediunsaturated acrylic or methacrylic esters or ethylenicallydiunsaturated acrylic or methacrylic amide derivatives, as well asunsaturated polyesters.

Of the monoethylenically unsaturated monomers, acrylic and methacrylicesters, acrylonitrile and lower vinyl erally speaking these do not havea deleterious elfect on the process.

In carrying the new process into efl-ect in general solvents oremulsions and dispersions of monomers in such liquids or solvents areprepared, which on cooling solidify in crystalline form. By partialcrystalline solidification" we understand the partial solidification ofthe solvent in crystalline form and not the crystallization of themonomer from the solutions without the simultaneous separation ofsolvent crystals. The monomer content of these solutions and emulsionsor dispersions can vary within wide limits. Monomer solutions generallycontain between 1 and 20, preferably between 2 and by weight, based onthe solution. When the monomers are used in emulsified or dispersedform, they are generally used in amounts between 0.1 and 20, andpreferably between 0.5 and 10% by weight, based on the monomer emulsionor dispersion, but in special cases it can be higher than 20% by weight,e.g., 35% by weight. As liquids or solvents primarily those are usedwhich undergo crystalline solidification in the range of +100 to --100C., or preferably +25 to 25" C. Examples of these are acetic acid,dioxane, trioxane, benzene and in particular water.

When the monomers are used in the form for example of aqueous emulsionsor dispersions, the customary emulsifying agents and if desiredprotective colloids can be used in the emulsions or dispersions. Suchemulsifying agents are for example fully described in Houben-Weyl,Methoden der organischen Chemie, 'vol. XIV/ 1, Makromoleculare Stolfe,Georg Thieme Verlag, Stuttgart, 1961, in particular pages 192 to 208.Suitable compounds are for example anionic emulsifying agents, such asthe alkali metal salts of fatty acids, the alkali metal salts of acidaliphatic alcohol-sulfuric acid esters, in particular sodium sulfonate,alkali metal and ammonium salts of alkyl and alkylarylsulfonic acids,salts of fatty acid condensation products with oxyalkylcarboxylic acids,aminoalkyl carboxylic acids and in particular alkali metal salts ofsulfonated ethylene oxide a-dducts of aliphatic alcohols oralkylphenols, which for example contain'5 to 30, and in particular 8 to20, ethylene oxide groups, as well as cationic emulsifying agents, suchas salts of alkylamines, aryl, alkylaryl or resin amines and quaternaryammonium compounds, such as N-dodecyl-N-trimethylammonium chloride.Furthermore, there may be used non-ionic emulsifying agents, e.g. thereaction products of alkylene oxides, such as ethylene oxide, withaliphatic alcohols or alkyl phenols, whose alkyl groups preferablycontain from 8 to 12 carbon atoms. Mixtures of emulsifying agents, forexample mixtures of non-ionic and anionic emulsifying agents, may alsobe used for the process. The emulsifying agents of the type mentionedare generally present in an amount between 0.1 to 10% by weight, basedon the total monomer content, and preferably in an amount between 0.1and 5%. by weight. In particular instances the process may also becarried out without the addition of an emulsifying agent.

When light initiators are used it is advantageous to add to thesolutions, emulsions or dispersions, small quantities ofphotoinitiators, that is compounds which are decomposed into radicalsunder the action of light or which form radicals as a result ofreactions, these radicals acting as polymerization initiators. Suitablephotoinitiators are for example vicinal ketaaldonyl compounds, such asdiacetyl and benzil, aketaldonyl alcohols, such as benzoin, acyloinethers, such as benzoinmethyl ether and a-substituted aromatic acyloincompounds, such as a-methylbenzoin, aromatic ketones and aldehydes, suchas benzophenone, propiophenone or benzaldehyde. Such photoinitiators aregenerally added in amounts of 0.001 to 10% by weight, and preferablyfrom 0.01 to 3% by weight, based on the amount of monomers.

With these new processes the customary inorganic sensitizing agents (asdescribed in detail in the book of I. Kosar, Light-Sensitive Systems,John Wiley, New York, N.Y., U.S.A., 1965) may be used. Suitablecompounds are for example, heavy metal salts, e.g. iron, cobalt, nickel,

mercury, zinc, titanium, tin, cadmium, lead, thallium, silver, gold anduranyl compounds; oxides of zinc and titanium, and salts of tin, such astin(II) chloride, fluoride, bromide, iodide, sulfate, acetate, adipate,cinnamate, benzoate, acrylate, octoate and furthermore the diflicultysoluble tin(II) hydroxides; lead tetraethyl and thallium nitrate as wellas the sulfides and oxylates of zinc, strontium and silver, and theoxalates of cadmium and mercury. Particularly suitable are the uranylsalts, such as uranyl nitrate and uranyl salts of organic acids, such asuranyl acetate. The salts of iron, cobalt or of nickel can be used assuch. The combination of metal ions with variable valencies withperoxides, such as hydrogen peroxide, persulfates and organic peroxycompounds is particularly advantageous. Complex salts can also be usedwith advantage, such as iron(III) ammonium citrate, tartrate or oxalate.The amounts of inorganic sensitizing agents can in general be between0.01 and l, and preferably between 0.1 and 0.2% by weight, based on thetotal amount of solvents. In addition to the inorganic sensitizingagents of the type cited organic sensitizing agents of the typementioned above can also be used. Furthermore, it is frequentlyadvantageous to use in addition to the inorganic sensitizing agents,peroxides, in particular hydrogen peroxide or persulfates, such aspotassium persulfate, the amount of such peroxides being between and500% by weight, based on the amount of inorganic sensitizing agents orphotoinitiators.

In addition to the photoinitiators the solutions, emulsions and/ordispersions of the monomers can with advantage contain polymers, inparticular polymeric synthetic resins in solution or in the form of adispersion.

Suitable high polymeric synthetic resins, which generally have amolecular weight greater than 10,000, are all synthetic high polymersobtained by conventional polymerization and polycondensation processes,which are soluble or dispersible in the solvents used in the new processor which can if desired, be present in a dispersed state, as when thepolymers are obtained by an emulsion polymerization process. Suitablecompounds are for example homoand/or copolymers of monoand/ordiolefinically unsaturated monomers, e.g. of monoor diolefins withpreferably 2 to 5 C atoms, such as ethylene, propylene, isobutylene,butadiene, chloroprene and isoprene, of a,;3-ethylenically unsaturatedmonoand dicarboxylic acids, in particular with 3 to 5 C atoms, such asacrylic acid, methacrylic acid, maleic acid and itaconic acid and/oramides or substituted amdies, nitriles and/ or esters thereof, inparticular those of alkanols containing 1 to 8 C atoms, such as themethyl, ethyl, propyl, n-butyl, tert-butyl, n-hexyl and Z-ethylhexylesters of acrylic and methacrylic acids and diethyl anddi-n-butyl-maleate and acrylamide, methacrylamide, N-methylolmethacrylamide and N-n-butoxymethyl acrylamide, acrylonitrile andmethacrylonitrile, of vinylaromatic monomers, such as styrene,a-methylstyrene, divinylbenzene and vinyltoluenes which in generalcontain only 1 benzene nucleus, of vinyl esters of saturatedmonocarboxylic acids which in general contain from 3 to 12 C atoms, inparticular vinyl acetate, vinyl propionate, vinyl butyrate and vinyllaurate, of vinyl halides, in particular vinyl chloride, vinylidenechloride and vinyl fluoride, of vinyl ethers, in particular alkanolscontaining 1 to 4 C atoms, such as vinyl methyl ether and vinyl isobutylether, of heterocyclic vinyl compounds, such as vinyl pyridines, N-vinylpyrrolidone and N-vinylimidazolium salts, e.g.N-vinyl-N-methylimidazolium chloride and N-vinyl-N-methylimidazoliummethosulfate. Suitable high polymeric synthetic resins are in additionfor example the saturated polyesters manufactured in conventionalmanner, and in particular polyethyleneglycol terephthalate,polyurethane, and in particular the polycondensation products ofhexarnethylene diisocyanate and alkanediols, such as glycol and 1,6hexanediol, synthetic polyamides with recurring units of the generalformula CONH in the chain molecule,

such as poly-e-caprolactam, polylaurolactam and polycondensationproducts of aliphatic dicarboxylic acids, such as adipic acid or subericacid and of aliphatic diamines, such as hexamethylene diamine,decamethylene diamine and 4,4'-diamino-dicyclohexylmethane, polyvinylalcohols and modified products thereof, polyalkylene oxides, such aspolyethylene oxides and polypropylene oxides, in particular with adegree of polycondensation greater than 10, polyacetals, such aspolyformaldehyde, furthermore polycarbonates, polyureas, celluloseesters and ethers, in particular cellulose acetate and also polyimides,such as polyethylene imine.

The polymers and polycondensation products of the type mentioned can bemanufactured in customary manner and they may be used in solution or indispersion. Solution or emulsion polymers, e.g. in the form in whichthey are obtained in solution or dispersion polymerization, can be usedwith advantage. Solutions or dispersions can also be used which areprepared from the polymers or polycondensation products, e.g. frompolyethylene, synthetic polyarnides, polyalkylene oxides orpolyformaldehyde. In the preparation of synthetic resin dispersions byemulsion polymerization or by so-called secondary dispersions,emulsifying agents or protective colloids can also be added, for exampleas described fully in Houben- Weyl, Methoden dor organischem Chemie,XIV/ 1, Makromolecular Stoffe, Georg Thieme Verlag, Stuttgart, 1967, inparticular on pages 192 to 208. Of particular interest are additives ofthose synthetic resin dispersions which are used as bonding agents, inparticular as bonding agents for nonwoven fabrics, e.g. those based oncopolymers of acrylic and methacrylic acid esters, butadiene and vinylesters.

Of particular interest are furthermore additives which are solutions anddispersions of vinyl chloride homopolymers and copolymers, styrenehomopolymers and copolymers, polyisobutylene, synthetic polyarnides,polyurethanes, polyvinyl pyrrolidone, polyacrylic acid and copolymers ofacrylamide and acrylic acid in water or organic solvents, such asglacial acetic acid, dioxane and benzene.

The amount of high polymeric synthetic resin of the kind mentioned abovepresent in the monomer solutions and emulsions or dispersions can varywithin very wide limits. It is generally between 0.1 and 50, andpreferably between 1 and 30% by weight, based on the monomers. Thesolutions and dispersions of the synthetic resin can be added to themonomer solutions, emulsions or dispersions in general as a 0.1 tosolution or a to 60% dispersion (in weight percent, based on thesynthetic resin solutions or dispersions). When polymeric resins insolution or in the form of a dispersion are added, the data given forthe monomer concentrations in the mixtures containing the monomers,solvents and synthetic resins refer to the total content of the mixture.

The solutions and emulsions or dispersions of the monomers are thensolidified or partially solidified in crystalline form. This can beeffected for example by using a cold base, such as a cold endless beltor a cooling roller, or on the cold surfaces of molds or on premoldedform to be fiber-coated, such as plastic sheets, textiles and leatherarticles, and if desired by cooling both surfaces of these structures,in particular when they are laminar structures. Nonwoven fabrics made ofnatural or synthetic organic or inorganic fibers can with advantage besoaked in or impregnated with these solutions and the solutions andemulsions or dispersions solidified or partially solidified in partiallycrystalline form. In this manner generally more than 50 and preferablymore than 60% by weight of the monomer solutions, emulsions and/ordispersions are solidified in crystalline form.

According to another embodiment of the new process, cooling can beeffected between two cooled endless metal belts or two cooling rollersor in a particularly advantageous manner in a cooled gap. The distancebetween the cooling surfaces, for example the distance between thecooling bands or cooling rollers and furthermore the space between thecooling surfaces of the cooling gap is generally less than 5 cm. In somecases it is advantageous for the/process to be effected with a distancebetween the cooling surfaces or more than 5 cm. Generally speaking thedistance between the cooling surfaces is from 0.5 to 10 mm., and inparticular between 1 and 5 mm. Preferably the cooling areas havesurfaces with bad wetting properties, in particular when using two ormore cooling rollers or cooling gaps. When using cooling gaps, thelength of the latter can vary within wide limits.

The solutions or emulsions, and the forms impregnated with the latterare advantageously present in the form of flat structures, generally asbroad bands, with a width generally between 0.1 and 3 mm. and athickness generally between 0.5 and 20 mm., in particular between 1 and10 mm. In some cases it is advantageous for the solutions or emulsionsof the monomers or the woven or non-woven.

fabrics impregnated wtth the latter to be conveyed for cooling andirradiation treatment through a flat or flattened tubular sheeting, madefor example from polyethylene. In this case the cooling can be effectedin a particularly simple manner in a cooling bath. The process can becarried out continuously or in batchwise manner.

The solutions and emulsions or dispersions solidified or partiallysolidified in crystalline form are then subjected to irradiation.Preferably lamps providing energy-rich light, in particular light with awavelength of 200 to 500 m are used, e.g. carbon arc lamps,mercury-vapor lamps, xenon lamps or fluorescent strip lamps. Daylightand sunlight can also be used. In addition ionizing radiation is alsosuitable, e.g. electron beams, X-rays, as well as mixed rays, as emittedby radioactive materials, e.g. by nuclear fuel elements. The duration ofthe radiation can vary within wide limits. It is all the shorter, thehigher the energy level of the radiation and the higher the radiationdensity. In some cases several seconds of irradiation are sufficient,e.g. when using electron beams with a high radiation density. In someinstances radiation times of several minutes are necessary, e.g. whensun rays are used for the irradiation. When using rays with a highenergy level, e.g. electron beams or quartz-UV rays, photoinitiatorsneed not be present. Incontrast to this photoinitiators are need whenradiation is effected with longer wavelength light in the visible andnear-ultraviolet range of the spectrum, in conformity with theabsorption of the materials to be polymerized.

The monomers are polymerized as a result of the irradiation. Monomerconversion in the polymerization is between 50 and or higher. After thepolymerization the solvents and any residual monomers are separated fromthe fibrous polymers or poromeric materials obtained, and they can bereused. To effect this the reaction products can for example be heated,to melt the crystallized solvents and the latter can then be removed forexample by filtration, centrifuging and/or evaporation. The separationof the solvents can also be effected under reduced pressure.

In the hitherto known process for the production of polymers frommonomers containing at least two polymerizable double bonds, in generalextremely brittle materials were obtained with glass-like properties,which easily disintegrated or which were in powder form, unlessconsiderable amounts of monoethylenically unsaturated monomers wereadded. Such polymers could only be used in special technical fields,e.g. as ion exchange materials. The production of fibers from suchpolymers was not possible'. In contrast to this it is possible by theprocess of the present invention to obtain polymers directly in the formof fibers from any desired monomer or mixtures of monomers, if theycontain at least 0.01% and in particular at least 0.5% by weight ofmonomers with at least two polymerizable double bonds. This opens up anew range of possible applications, e.g. woven and non-woven textilematerials, as well as plastic sheets can be coated with fibers on one orboth surfaces according to the new process, forming a velvety deposit onthe textiles and plastic sheets. If non-woven fabrics, e.g. based onrayon staple fibers, polyamides orpolyesters are impregnated in themanner described above and the solution of the monomers in admixturewith the non-woven fabric is brought to crystalline solidification andis irradiated, after separating the solvent and excess monomers,products are obtained which are velvety and leather-like in theirproperties, which we call poromeric materials. Such products can beobtained in various colors when colored monomers" are used for theprocess.

The products obtained according to the new invention can for example beused as floor coverings, insulating materials for heat insulationespecially at high temperatures and as substitutes for leather, andfurthermore as coating materials. If monomer mixtures containing a highproportion of monomers with atleast two polymerizable double bonds areused, e.g. containing more than 50% by weight thereof, based on thetotal monomer content, fibrous polymers with particularly good thermalstability are obtained.

Poromeric materials with particularly good fastness to rubbing areobtained according to the new process, for example, when the nonwoventextile fabric impregnated with monomer solutions or emulsions and inthe form of a flat structure is cooled on both surfaces and/or when aspolyethylenically unsaturated monomers unsaturated polyesters are usedalone or in admixture and/or high polymeric synthetic resins in solutionor in dispersion are used in addition to the monomer solutions oremulsions.

In the examples which follow the parts given are parts by weight. Theacid numbers are determined as laid down by DIN 53,402 and thepercentages given are by weight.

EXAMPLE 1 20 parts bis-N-methylolacrylamide ethylene glycol ether aredissolved in 200 parts glacial acetic acid. The solution is cooled to 25C., whereupon the mixture is solidified in crystalline form. Thesolidified solution is irradiated for 2 hours with a commercial mercuryhighpressure lamp (125 w.). After thawing out has occurred, the fibrouspolymer obtained is separated from the glacial acetic acid bycentrifuging, Washed with water and dried. Seven parts of a colorlessfibrous product are obtained with a softening point above 350 C., whichcan be used as an insulating packing material.

If bis-N-methylolacrylamide ethylene glycol ether is replaced by thesame quantity of 1,4-butanediol diacrylate, but the same operatingconditions are used in other respects, 7.5 parts of a colorless fibrouspolymer with a softening point of about 350 C. are obtained. The fibersare suitable as materials for heat insulation at elevated temperatures.

EXAMPLE 2 A solution of 300 parts bis-N-methylolacrylamide ethyleneglycol ether and 15 parts benzoin methyl ether in 2700 parts glacialacetic acid are poured into a vat cooled to 20 C., which is covered witha non-woven fabric made of rayon staple weighing 50 g./m. The solutioncovers the fabric completely. After the solution has solidified incrystalline form, irradiation is carried out from a distance of 50 cm.by two commercial mercury high-pressure lamps situated in the focalpoint of a parabolic mirror. This is followed by heating to roomtemperature, draining off the glacial acetic acid and excess monomers,washing with water and drying. A product with velvety properties isobtained, with the fibrous polymers arranged vertically over the staplefibers of the non-woven fabric.

If in place of the above-mentioned glacial acetic acid solution asolution of 30 parts benzoin methyl ether and 300 partsmethylene-bis-acrylamide or 1,4-butanediol diacrylate orm-xylylene-bis-acrylamide or trimethylene glycol diacrylate in 2700parts glacial acetic acid are used 10 under otherwise identicalconditions, a velvety material is likewise obtained which is verysimilar in appearance to the material described above.

In place of the rayon staple non-woven fabric a fiberglass fabric canalso be used. A velvety material is also obtained in this instance.

EXAMPLE 3 A non-woven fabric of polyester fibers is steeped in a vatwith a solution of parts m-xylylene-bis-acrylamide, 100 partstriethylene glycol diacrylate, 100 parts bis-N-methylolacrylamideethylene glycol ether and 300 parts benzoin methyl ether in 2700 partsglacial acetic acid in such a manner that the fabric is completelycovered by the solution. Cooling, irradiation and processing is carriedout as described in Example 2. A velvety material is obtained, which ischaracterized by a high mechanical resistance.

EXAMPLE 4 Rayon staple non-woven fabric is wound around the lamp-chimneymade of glass of a dipping lamp arrangement. The non-woven fabric isthen immersed in a solution which contains 810 parts glacial aceticacid, 4.5 parts benzoin methyl ether and in addition (a) 90 parts of amixture of equal parts divinylbenzene and bis-N- methylolacrylamideethylene glycol ether or (b) 90 parts allyl acrylate or (c) 90 parts ofa mixture of equal parts 1,4-butanedio1 diacrylate, m-xylylenediacrylate or (d) 90 parts of a mixture of equal parts 1,4-butanedioldiacrylate and acrylamide or (e) a mixture of 45 partsm-xylylenebis-acrylamide and 19 parts acrylamide.

The solution is cooled to 5 to 0 C., causing the solution to solidify incrystalline form. This is followed by irradiation for minutes with acommercial mercury high-pressure lamp, heating until the glacial aceticacid has melted, draining off any liquid, washing with water and drying.A velvety material with a high thermal stability is obtained, which issuitable for thermal insulation.

A similar material is likewise obtained when using a solution of 16.6parts m-xylylene-bis-acrylamide and 1.7 parts benzoin methyl ether in810 parts glacial acetic acid under operating conditions which otherwiseare the same as described above.

EXAMPLE 5 Solutions of 45 parts allyl acrylate or 22.5 partsmxylylene-bis-acrylamide and 2.2 parts benzoin methyl ether in 800 partsdioxane are subjected in the presence of a rayon staple non-woven fabricto crystalline solidification and irradiation in the manner described inExample 4. Poromeric fiber materials with a very pleasant handle areobtained.

EXAMPLE 6 Solutions of (a) 22.5 parts m-xylylene-bis-acrylamide, 10parts vinyl chloride and 2.25 parts benzoin methyl ether, (b) 4.5 partsbis-N-methylolacrylamide ethylene glycol ether, 72 parts ethyl acrylateand 0.9 part benzoin methyl ether, (c) 4.5 partsbis-N-methylolacrylamide ethylene glycol ether, 45 parts n-butylacrylate and 0.9 part benzoin methyl ether, (d) and (e) 4.5 parts allylacrylate or butanediol diacrylate, and 45 parts acrylic acid ethylester, and 0.9 part benzoin methyl ester in 800 parts glacial aceticacid are subjected in the presence of a rayon staple nonwoven fabric tocrystalline solidification and irradiation, as described in Example 4.After removal of the glacial acetic acid and drying, an absorbent fibermaterial with a handle similar to leather is obtained.

EXAMPLE 7 A solution of 45 parts bis-N-methylolacrylamide ethyleneglycol ether, 360 parts n-butyl acrylate and 4.5 parts benzoin methylether in glacial acetic acid (2700 parts) is divided into 3 portions;into 1 portion (a) there is placed a needleloom non-Woven fabric ofpolyhexamethylene adipamide weighing 80 g./m. and this portion isintroduced into a vat continuing the second portion (b) in which thereare placed two non-woven fabrics made of rayon staple, each weighing 50g./m. the vat being cooled to a temperature of 20 C. to effectsolidification, and this being followed by irradiation for minutes with8 blacklight lamps (Philips TL 40 W/08). A non-woven fabric made ofrayon staple is placed in the third portion of the solution and thetemperature is lowered to 20 C. to congeal the solution, whereuponirradiation with a 2 mev. Van de Gralf electron accelerator with a 25 m.radius is carried out. Sheets of fiber materials with a very soft handleand with closely similar appearance and handle are obtained.

EXAMPLE 8 A solution containing (a) 30 parts allyl acrylate, 30 partsbis-N-methylolacrylamide ethylene glycol ether, 240 g. n-butyl acrylateand 6 parts monomer (6 parts l-amino-2-acetyl-4-acryloylamino-anthraquinone) in 2700 parts glacial aceticacid, or (b) 120 parts vinyl isobutyl ether, 120 parts tert-butylacrylate, 30 parts bis-N-methylolacrylamide ethylene glycol ether, 30parts m-xylylene-bis-acrylamide and 6 parts blue-colored monomer (6parts 1- amino-Z-acetyl-4-acryloylamino-anthraquinone) is introducedinto a vat cooled to 20 C. into which is placed a non-woven fabric ofrayon staple. The non-woven fabric is completely covered by thesolution. The latter is solidified and irradiated with a 6 m. radiumelectron accelerator of 2 mev. Colored sheets of fibrous material with avery pleasant handle and similar in appearance to leather are obtained.

EXAMPLE 9 A solution of 30 parts bis-N-methylol acrylamide ethyleneglycol ether, 10 parts allyl acrylate and 1 part benzoin methyl ether in900 parts glacial acetic is placed into a vat cooled to 30 C. which islaid out with a non-woven fabric of rayon staple in such a manner thatthe fabric is covered by the solution. The latter is allowed to solidify1 2 which is flexible like leather and has good mechanical properties. I

EXAMPLE 10 A solution of (a) 100 parts N-vinyl caprolactam, 100 partsbis-N-methylol acrylamide ethylene glycol ether, 100 parts butanediolmonoacrylate and 3 parts benzoin methyl ether in 2700 parts glacialacetic acid or (b) 150 parts tertbutyl acrylate, 150 parts butanedioldiacrylate and 1.5 parts benzoin methyl ether in 2700 parts glacialacetic acid are introduced into a vat cooled to 20 C., which is laid outwith a needleloom non-woven fabric of rayon staple. The fabric is coatedwith solution (a) or (b). It is allowed to solidify and irradiated for10 minutes with 8 blacklight fluorescent tubes. After thawing out,removing the glacial acetic acid and washing with water, a fibermaterial that is highly resistant to abrasion is obtained.

EXAMPLES 11 TO 20 A needleloom non-woven fabric of cellulose fiber(weight of the fabric is 100 g./m. is impregnated with a solution of 0.1part benzoin methyl ether and solutions of monomers in 100 parts glacialacetic acid in amounts as given in Table 1 which follows. Theimpregnated fabric is introduced into tubular sheeting of polyethyleneand is compressed to a thickness of 0.3 cm. between two metal plates.The compressedarticle is then cooled for 1 to 2 minutes to 35 C. in acooling brine. The solution of the monomers thus solidifies incrystalline form. The solidified structure is then taken from thecooling brine, the metal plates are removed and both surfaces of thestructure are irradiated for 5 minutes with a Philips blacklight lamp TL40 W/08. This is followed by thawing out, the washing product severaltimes with water and drying. The monomers used and the amounts in whichthey are used, the polymer yields, and the tensile strength andelongation of the products obtained are summarized in Table 1 below.

Polymer yield in Tensile Elonga- Example Unsaturated monomers with 2olefinlc weight strength tlon in 0. Parts double bonds PartsMonoolefinic unsaturated comonomers percent (kg/em!) percent;

1.65 All lac late 5 Ethyl acrylate (I) N h H 18mm th 1 1 5i ITI-vlny1caprolactam n} 53 1.65 Bismet o-acry e e ene eel ether. y y g y i5 Vinylthioethanol (II) 5 55 1.65 Trlethylene glycol dlacrylate..; g 3934 1.65 All lacr late 10 T y y 1 Acrylic acid (111) 42 67 1. 65Bis-N-methylol acrylamide ethylene gly- 5 T 82 col ether. 5 TT 1. 65Trlethylene glycol dlaerylate....;.; 1(1) T 72 55 64 7 e 1. 65 do 2. 5Vinyl isobutyl etheri 2.5 Maleic anhydrlde 63 65 18 3.3 Allylacrylate... 10 Acrylonltrile 85 19 83 19 5 Commercial monomer-freeunsaturated 5 }Butyl acrylate, 3-ch1oro-2-hydroxypro- 85 69 polyesterLudopal P 4. 1. pyl acrylate. 20 1.65 Bls-N-methylol acrylamide ethylenegly- 3. 35 }6.5 Me hy fl y 3 3 col ether. Butanedlol monoacrylate.

I Based on the amount of monomer present.

Norm-In Example 20 water is used as solvent, the lnitiator and methylacrylate are emulsified in the solution.

in crystalline form, it is again lined with a rayon staple non-wovenfabric and a cold solution containing 70 parts n-butyl acrylate, 10 g.ethyl acrylate, 20 parts bis-N- methylol acrylamide ethylene glycolether and 0.25 parts benzoin methyl ether in 900 parts glacial aceticacid is added, so that the second layer of fabric is also covered by thesolution. The second layer is similarly allowed to solidify andthereupon a third layer of rayon staple fabric is applied and a cooledsolution of 80 parts n-butyl acrylate, 20 partsm-xylylene-bis-acrylamide and 25 parts benzoin methyl ether in 900 partsglacial acetic acid is poured in, so that the fabric is covered by thesolution. After this layer has also solidified in crystalline form, itis irradiated for 10 minutes with 8 blacklight fluorescent tubes. Thereis obtained a multilayer staple fiber sheet EXAMPLES 21 TO 26 1 solutionfor 10 minutes with a Philips blacklight lamp TL 40 W/08. This isfollowed by thawing out the solidified solution, washing the productseveral times with water and drying. The composition of the solutionsand the yields are summarized in the following table. In all casesfibrous materials with a high tensile strength and excellent fastness torubbing are obtained, which in addition have good sound-absorbent andheat insulating propused to impregnate needle-punched fabrics made ofcelluertres. lose fibers (weighing 100 g./m. and the flat objects TABLEPercent yield of polymer with regard Unsaturated polyesters produced incustomary manner Monoolefinically to the No. Parts from- Partsunsaturated monomers Solvent monomers 21.-.... 20 1 part maleicanhydride, 2 parts pthalic auhydride I Vinyl isobutyl ether- 3 partspropylene glycol (Acid N o. 30). 2g iii- Butyl agcrzlatei;h Glacialacetic 69 my iso u y e erii. I 8 r l i g i if Glacial acetic acid-....67

1 iny iso u y et er- V {mButyl acrylata Ethylene carbonate... 51

10 2 parts maleic anhydride, 1 part phthalic anhydride, Vinyl isobutylether-...

3 parts propylene glycol (Acid No. 48). 24. .r.;... 10 1 part maleicanhydride, 2.5 parts adipic acid, 1 part 30 n-Butyl acrylate- Glacialacetic acid 72 1l3Ihth2al)lc anhydride, 4.5 parts neopentyl glycol (Acid0. 25...-..:.-:..- 20 1 part maleic anhydrlde, 1 part phthalicanhydrlde, 2 20 Vinyl isobutyl ether....

parts adipic acid, 2 parts propylene glycol, 2.3 parts 30 n-Butylacrylate Glacial acetic acid..-.: 67 dipropylene glycol (Acid No. 31).10 Ch] h d 1 t ,.t. v v. 4 or y rmacryae-.. w 26. I T 35 mbuwl acwlatmGlacial acetic acid- 70 EXAMPLES 27 TO 30 obtained are cooled on a coldbase to -30 C., the solutions solidifying in crystalline form. These areirradiated A needleloom fabric made of cellulose fiber (weighing with aPhilips blacklight lamp TL 40 W/08 for 10 min- 100 g./m. on a cold baseis impregnated with a soluutes, are allowed to fill out, and theporomeric fabric tion of monomers and sensitizing agents in amounts as25 obtained is washed and dried. Poromeric materials are given in thefollowing table in 600 parts of solvent speciobtained w i have hightensile strength d fast ss fied in the following table. The impregnatedfabric is to rubbing, as Well as good thermal and heat insulating cooledon the base to a temperature of -30 C. The properties.

TABLE 4 High molecular weight synthetic Yield No. Parts Monomers Partsresins Solvent percent 31 8 Bis-N-methylol-acrylamide ethylene 1Polyethylene oxide (K value=2l0). Water 80 27 Chlorohydrin acrylate.- 328 Bis-N-methylol acrylami 1 Polyacryllc acid (K value=170) do 89 27Chlorohy n acrylate 33 8 Bis-N-methylol acrylaml 1 Polyethyleneimine(molecular weight do 86 27 Chlorohydrm acrylate about 3,000).

5 Triethyleue glycol diacryla 34 Cellulose acetate (content of acetateGlacial acetic 27. 5 Ethyl acrylate....-......-.....-....-.-... 3 groups53.5% (K value=900). acid. 72

2.5 Acrylic acid 5 Triethylene glycol diacrylate 61 35 27.5 Ethylacrylate 1 Polyvinyl chloride (K value=57) Dioxane....-;:

2.5 Acrylic i solution of the monomers thereupon solidifies in crystal-EXAMPLES 36 TO 38 line form. This is followed by irradiation for 5minutes with a Philips blacklight lamp TL 40 W/08, is allowed Themonomers given in Table 5 are dissolved in 600 to thaw out, and theproduct is washed several times with parts water, the dispersionsmentioned in Table 5 are water and dried with warm an. added and 0.3part benzoin methyl ether are d spersed TABLE Yield in sensitizingweight Parts Monomers Parts agents Solvent percent 25 Bis-N-methylolacrylamide ethylene glycol ether 0.7 Uranyl nltrate Water 94 45'Acrylamide- 25 Bis-N-methylol acrylamide ethylene glycol ether 0. 35 dodn 63 45 Acrylamide" Bis-N-methylol acrylamide 0.7 do dn 40 20Bis-N-methylol acrylamide ethylene glycol ether Ethyl acrylate- 5Acrylic i 2. 6 Tin (II) acetate... Glacial acetic acid- 53 10Triethylene glycol diacrylate The poromeric materials obtained haveexcellent thermal 6 therein with the aid of an impeller. Non-wovenfabrics insulalions and Sound absorbent P P are saturated with themixtures, as specified in Examples EXAMPLES 31 TO 35 31-35, and aresubjected to further processing as de- Solutions are prepared frommonomers and high molecscribed therein- The Yields in P y in Weight Pular synthetic resins in amounts as given in Table 4 and cent, based onthe monomers used, is given in Table 5 from 0.3 part benzoin methylether by using 600 parts 65 which follows of the solvent mentioned inTable 4. The solutions are TABLE 5 Yield,

No. Parts Monomers Parts Dispersion percent 16 B -N- eth lol acr lamideeth lene 1 col ether 15 407 dispersion of a copolymer of parts butylacrylate, 85 36 ls m y y y g y 7 parts acrylic acid and 3 partsbutanediol diacrylate,

' 30 N-methylol acrylamide.--.-. N-methylol acrylamide (5%).

37 8 1,4-bis-N-methylol acrylamide butanediol ether ll 55% dispersion ofa copolymer of 89 parts vinylrdene 56 21 Chlorohydrin acrylate chlorideand 11 parts methyl acrylate. 38 8 1,4-bis-N-methylol acrylamidebutanediol ether n} 12 50% dispersion of polyvinyl prop1onate. 43

21 1,4-butanediol monoacrylate 15 EXAMPLES 39 TO 44 removed from thecold base is washed and is dried at 25 C. The polymer yields and themonomers and emulsifying agents present the emulsions, as well as theamounts present are summarized in Table 6 which follows.

The poromeric materials obtained have a soft, leather like handle, ahigh absorptive capacity for water and excellent heat and soundinsulating properties.

1 6 Similar results are obtained by using in place of benzoin methylether as sensitizing agent a-methylol benzoin methyl ether, a-methylolbenzoin propyl ether, a-methylol benzoin, benzoin propyl ether, benzil,azo-bis-isobutyronitrile', diparatolyl disulfide or diphenyl disulfide.

EXAMPLE 55 7 One part polyacrylamide (K value in water at25 C.= 170) and0.15 parts sulfonated castor oil are dis-.

solved in 600 parts Water/ and 8 parts 1,4-butanediol di-.

acrylate and 21 parts 1,4-butanediol monoacrylate are emulsified in thesolution. 0.3 parts benzoin methyl ether are dispersed in the emulsionand this is used to impreg mate a needleloom rayon staple fabric (weight100 g./m.

The impregnated fabric is cooled on a belt-type metallic TABLE 6Monomers Yield in weight percent, based on the Parts Emulslfying agentsmonomers 10 1,4-butanediol diacrylate.

1,4-butanediol monoacrylate- 0.5 Sulfonated castor oil 73 30 Methylacrylate. 10 Allyl acrylate 1,4-butanediol monoacrylate. 30 Methylacrylate 0.5 Sodium stearate 10 Triethylene glycol diacrylate Ethylaerylate.

0. 5 Sulfonated castor oil.

5 Acrylic acid 10 1,4-butanediol diacrylate 1 l-butanediol monoacrylate.40 inyl propinnato N-butyl acrylate.

Unsaturated polyester A from 1 part rnaleie acid, 1 part phthalic acid,2 parts adipic acid, 2 parts propylene glycol and 2.3 parts dipropyleneglycol Vinyl isobutyl ether;

Unsaturated polyester A Vinyl thioethanol. 30 Ethyl acrylate.

EXAMPLES 45 to 54 The monomer amounts given in Table 7 which follows 40are used in 600 parts water, and sulfonated castor oil is added inamounts as specified in Table 7, for emulsification 0.3 part benzoinmethyl ether are added for the dispersion, as well as the amounts ofsynthetic resin dispersions as specified in Table 7.

The needlesloom non-woven fabrics made of cellulose fibers (weighing 100g./m. are impregnated with the mixtures obtained. This mass is subjectedto crystalline solidification on a cooled belt-type metallic base at atemperature of -30 C. The solidified objects are thereupon subjected toa thawing process and the poromeric materials obtained are separatedfrom the base, washed and dried at C. The polymer yields are given inTable 7. The poromeric materials have a soft, leather-like handle, ahigh absorptive capacity for water and excellent heat and soundinsulating properties.

base at a temperature of C. until the emulsion solidifies. This mass isthen irradiated for 10 minutes with a Philips blacklight lamp TL W/08,this is followed by thawing out, the poromeric material is removed fromthe base, washed with water and dried at 25 C. The yield in polymer is80% by weight, based on the monomers.

EXAMPLES 56 to 58 The monomers mentioned in Table 8 are emulsified byadding 0.35 parts sulfonated castor oil in 600 parts water and thesensitizing agents specified in Table 8'are' added" thereto.Needle-punched rayon staple fabrics (weight per unit area 100 g./m. areimpregnated with the mixtures thus obtained and the resulting materialsare subjected to further procesing as described in Example 55.

The polymer yields obtained, based on the monomers used, are given inTable 8.

TABLE 7 Yield in weight per- Parts sulcent, based tonated on the N 0.Parts Monomers castor oil Parts Synthetic resin dispersion monomers i233:23:38} g gf g gg gf gj:: 0.5 35 50% aqueous dispersion ofpoly-n-butylaeryla e 69 5 Triethylene glycol diacrylate.. 0.25 15 40%aqueous dispersion of a copolymer of 85 parts butyl- 22 Ethyl acrylateacrylate, 7 parts acrylic acid 3 parts 1,3-butanediol diacry- 89 15Acrylic acid late and 5 parts N-methyloi acrylamide. 7

2? htguzauegol diacrylatef.t.. 0 25 5 do 92 u ane o monoaery a e 2Triethylene glycol diacrylate 0. 25 aqueous dispersion of a copolymer of89 parts vinylldene 91 27 Ethyl acr alate chloride and 11 parts methylacrylate.

8 1,4-butanediol diacrylte--. 0 25 do 86 21 ig t-butanediol monoacryla 71 N flzgggggj gags; 0. 35 10 50% aqueous polystyrene dispersion V 50 28ggfigfgggggfiKI 0.7 10 aqueous polystyrene dispersion 50 2 gzglggg gi gg g ggfi g: 0.25 10 50% aqueous dispersion of polyvinyl proprionate.-..."83 26 g f gg ffgg 0. 35 10 50% polyvinyl chloride dispersion. g 0- 540% p y y dispersion 5 I l 0.5 dn 40 l i TABLE 8 Yield, weight MonomersParts sensitizing agents percent Allyl acrylate 1 23 1 lg 0. 35 Thalllumnitrate 25 y aery e Ethyl acrylateu 0.35 Zinc olfide 35 A11ylaery1ate.0. 175 Potassium ferric oxalate 80 n-Butylacrylate 0.7 Cumenehydroperoxide We claim: 10 contain at least 5% by weight of saidmonomers with at 1. A process for the production of polymeric materialhaving a fibrous poromeric structure and being reinforced with anon-woven fabric which comprises:

(a) dispersing ethylenically unsaturated monomers in a liquid whichliquid undergoes crystalline solidification at a temperature between--100 and +100 C., at least 0.01% by weight of said ethylenicallyunsaturated monomers containing 2 or more polymerizable double bonds,said monomers containing 2 or more polymerizable double bonds beingselected from the group consisting of polyethylenically unsaturatedcarboxylic esters, polyethylenically unsaturated acid amides,polyethylenically unsaturated ethers, polyethylenically unsaturatedamines and polyethylenically unsaturated polyesters;

(b) combining said monomer liquid dispersion with a non-woven fabric;

(0) cooling said liquid suificiently to crystallize at least 50% of saidliquid, said liquid containing said dispersed monomers being combinedwith said fabric so that on cooling a frozen band is formed;

(d) irradiating said frozen band by high-energy light or ionizingradiation until the monomers are polymerized;

(e) thawing said frozen band; and

(f) separating the resultant non-woven fabric reinforced polymericmaterial from said liquid.

2. A process as in claim 1 wherein said liquid undergoes crystallinesolidification at a temperature between -25 and +25 C.

3. A process as in claim 1 wherein said band has a thickness of from 1to mm.

4. A process as in claim 1, wherein the frozen structure is irradiatedby light with a wavelength of from 200 to 500 mil.-

5. A process as in claim 1 wherein water is used as the said liquid.

6. A process as in claim 1 wherein the said monomers contain at least0.5% by weight of said monomers with at least two polymerizable doublebonds.

7. A process as in claim 1 wherein the said monomers least twopolymerizable double bonds.

8. A process as in claim 1 wherein said ethylenically unsaturatedmonomers include monoethylenically unsaturated monomers selected fromthe group consisting of acrylic esters, methacrylic esters, acrylamidesand methacrylamides.

9. A process as in claim 1 wherein said monomers containing 2 or morepolymerizable double bonds are selected from the group consisting ofdiesters of diols with 2 to 10 carbon atoms with acrylic acid, diestersof diols with 2 to 10 carbon atoms with methacrylic acid, and allylesters of saturated or monoolefinically unsaturated dicarboxylic acidscontaining 3 to 8 carbon atoms.

10. A process as in claim 1 wherein said monomers containing 2 or morepolymerizable double bonds are selected from the group consisting ofdiacrylic and dimethacrylic esters of diols having from 2 to 10 carbonatoms, and allyl acrylate.

11. A process as in claim 9 wherein said ethylenically unsaturatedmonomers include monoethylenically unsaturated monomers selected fromthe group consisting of acrylic or methacrylic esters of alkanols havingfrom 1 to 8 carbon atoms, monoacrylic or monomethacrylic esters of diolshaving from 2 to 6 carbon atoms, and said esters wherein the alcoholresidue in the ester contains a dialkylamino group.

References Cited UNITED STATES PATENTS 3,092,512 6/1963 Magat et al117-9331 3,376,158 4/1968 Buser 117-1192 3,607,692 9/1971 Sanner et al117-9331 3,640,753 2/ 1972 Krauch et a1. 117-119.2

WILLIAM D. MARTIN, Primary Examiner J. H. NEWSOME, Assistant ExaminerUS. Cl. X.R.

117-1192, 126.6 B, 135.5, 138.8 F, A, 145, 161 UZ, 161 K; 161 UN, 161UC, 161 UT; 204-15922;

v UNITED STATES PATENT OFFICE CERTIFICATE- OF CORRECTION Patent No. 82%Dated December 11. 1975 lnv n fl Carl Heinrich Krauch and Axel Sanne rIt is certified that error appeal-sin the above-identified'patent andthat said Letters Patent are hereby-corrected as shown below:

Column 2, line +3, "monolefinically" should read monoolefinically Column7, lines 26-27, "Makromolecular" should read Makromo'leculare col n 8,line 1L9, "wtth" should read with?" Column 9, line 75 .,ff't imet yienhem seed -.5- 'triethylene Column 11, line 1, "continuing" should read65-; containing Columns 11 '12, lines lO-6O, Table, example "7" shouldread l7 and fourth column heading "Parts" ,second occurence,

example 20, insert 6.5 below "1.65" and above "5.55",

and fifth column, heading "Monoolefinic unsaturated .ycomonome'rs",example 20, delete "6.5" before "Methyl acrylate" Columns 13-14, lines3-20, Table, seventh column, example 21, p "69" should read 66 --b e IColumn 16, line 55, "procesing" should read -processing V Signed andsealed this 3rd day of December 1974.

(SEAL) Attest: p MecoY M. GIBSON JR. c. MARSHALL I-DANYNY attesting;Officer 7 Commissioner of Patents i Foam Po-mso (10-69) I USCOMM-DC60376-P69 w us, coyuuusur manna omen 19a 0-368-384.

